Resinous material



A ril 2, 1946. I I L. GERHART 2,397,600

- RESINOUS MATERIAL Original Filed Marc-nae, 1940 2 Sheets-Sheet, 1 r

Y Ho W420 L GEEHHET Patented Apr. 2, 1946 2,397,600 v ansmous MATERIALHoward L. Gerhart, Milwaukee, Wis assignor to Pittsburgh I Plate GlassCompany, Allegheny County, Pa., a corporation of Pennsylvania Originalapplication March is, 1940, Serial No.

324,392. Divided and this application September 17, 1943, Serial No.502,727

8 Claims. (01. 260-423) The present invention relates to the artificialresins, and it has particular relation tothe manufacture of artificialresins from diene hydrocarbons.

One object of the invention is to provide a resin which is inexpensiveto prepare, readily soluble in cheap hydrocarbon solvents to providevarnishes that upon application to wood, metal, or other surfaces,readily dry in the air and, subsequently, quickly harden to firm,strongly adherent films which are inert in alcohol and other solvents,and are relatively chemically inert with respect to food products, andsimilar materials.

cyclopentadiene mixed with dicyclopentadiene occurs in considerableproportion in drip oils and other fractions in certain of the productsobtained in the cracking of petroleum hydrocarbons, in the production ofcarbureted water gas, and in the refining of coal tars. Thecyclopentadiene and dicyclopentadiene can be obtained in relatively pureform from these sources by distillation. The mixture of monomer anddimer as thus obtained, has heretofore been subjected to heating inorder to pyrogenetically decompose the dimer to form the monomer. It hasbeen suggested to treat the resultant cyclopentadiene with a catalystsuch as the halide of an amphoteric metal in order to induce at a lowtemperature a peculiar type of reaction in which hydrocarbon moleculesare linked together in complex chains, in which the molecules of thecatalyst act as connecting links. When the reaction product is treatedwith alcohol, a polymer of the hydrocarbon is split off. The resultantpolymer has been described as a rubber-like product which is insolublein hydrocarbon solvents, and which upon exposure to the atmosphere,eventually degrades into a powder-like material. It has been suggestedto work this powdery material up with suitable plasticizers or softenersin order to form a composition suitable for use as lacquers. However,insofar as at present is known, such process has never received anycommercial application. The rubbery masses as heretofore initiallyobtained by treating cyclopentadiene with a catalyst, since they areinsoluble, are quite unsuitable for use as lacquer forming constituents.

The present invention is based upon the discovery that by proper controlof certain of the conditions involved in the production of polymers ofcyclopentadiene hydrocarbons, it is possible to produce resin-likebodies which are new chemical entities and are in contrast to knownmaterials. For example, they do not require the cyclopentadiene fromdicyclopentadiene has use of alcohol to effect formation of a polymer.They do not resemble rubber. They are relatively soluble in practicallyall of the ordinary hydrocarbon solvents. and upon exposure to theatmosphere, do not decompose or degenerate into powders. Films of theresin do not degenerate but instead maintain their continuity althoughthey oxidize to hard, adherent state. Accordingly, the resins are suitedfor use as film-forming ingredients in lacquers and varnishes and formany other uses, e. g., for molding, casting, as adhesives and the like.

As above stated, dicyclopentadiene, from which cyclopentadiene isreadily derived, is obtained mainly from three sources, namely, from thecracking of petroleum hydrocarbons, from domestic gas production, andlastly from the coal tar industry. The material ha heretofore been oflittle or no commercial value, and has in most cases not been separatedfrom the fractions containing it. The laboratory method of obtainingheretofore involved heating in a flask, and separating the monomer bydistillation. The meth- 0d, however, is relatively inefficient and only10w yields of the cyclopentadiene can be obtained by the applicationthereof.

A method has now been developed, whereby dicyclopentadiene fractions, asobtained from the above-designated industries, can be converted inalmost quantitative yields into cyclopentadiene suitable for conversioninto highly useful resins in accordance with the provision of thepresent invention. The method involves as one feature admixingdicyclopentadiene fractions with paraflin oil having a boiling pointwhich is above that of dicyclopentadiene, and distilling off from theresultant solution a mixture of dicyclopentadiene and cyclopentadienevapors which are subsequently passed through a heated tube in orderfurther to decompose the dicyclopentadlene into cyclopentadiene. Thenthe dicyclopentadiene which is not decomposed into cyclopentadiene iscondensed and returned to the distillation flask. The cyclopentadiene ofcourse is of relatively low boiling point, and can easily be separatedfrom the dicyclopentadiene material.

cyclopentadiene is subjected to polymerization in accordance with thefollowing procedure: cyclopentadiene is dissolved in a hydrocarbonsolvent such as gasolene or benzene or other solvents to provide asolution containing from 40% to 70% (more or less) of solvents. Thissolution is then warmed up at least to room temperature, or perhapsroughly to a temperature and a suitable catalyst is added in anappropriate amount. Various catalysts may be employed, among which maybe included halides of amphoteric metals. These include tintetrachloride, or bromide, Or iodide, and the like. Chlorides ofantimony, bismuth and aluminum, as well as for preparing polycyclo fromcyclopentadiene.

Its use may be described as follows:

To a solution consisting of a mixture of 1 part by weight ofcyclopentadiene and one part by volume of an inert hydrocarbon such asbenzol, toluol, petroleum, hydrogenated petroleum or chlorinatedhydrocarbons, is added no more than /50 part by volume ofdihydroxyfluoboric acid at 35 C. The solution is stirred to produceintimate mixture of the catalyst and cyclopentadiene. After about 3 to 5minutes, the temperature will rise to 50 then to 60 and perhaps to 80 C.If cooling is provided, the temperature may not rise above 50 C. Theliquid will thicken as the polycyclopentadiene forms and will assume adark brown, cloudy appearance. If the amount of catalyst used is notexcessive, about 50 to 70 per cent of the theoretical amount of resinwill be formed. If the cooling means is very eflicient, the temperaturemay not rise above 50 C. and the amount of resin formed is decreased,After the cooling means is removed, the temperature will rise from 50 toas high as 80 C. if permitted, or it may be caused to do so rapidly byadding more catalyst and mixing.

An infinite number of temperature conditions and catalyst concentrationscan be used in the reaction but in general it is desirable to keep thefirst peak of the temperature rise at 5060 Crso as to prevent a profuseboiling of the cyclopentadiene. This is accomplished by cooling, On thesecond temperature rise, which starts after the cooling bath is removedor when more catalyst is added, the peak may go as high as 120 C. but itis preferred to limit it to 80 C. by cooling. This latter temperaturerise is desirable, however, and it is preferred to heat the resinsolution after the polymerization is substantially complete to effect afinal cure.

The new catalyst has the following advantages:

1. It does not react below 30 C. for the above concentration ofcyclopentadiene used, thus permitting an easy control since merelycooling the solution sufiiciently will inhibit the reaction.

2. The amount of catalyst required is less than 2,897,600 of 30 to 60 0.and preferably to 40 to 50" c.,'

'7. The resin formed is free from poisonous lm= purities.

Ferric chloride admixed with a little hydrogen chloride is also ofinterest as a catalyst, because its use results in a resin of relativelylight color.

This catalyst may be used as follows:

Example 1 To 400 grams cyclopentadiene and 600 c. c. of toluene wasadded 3 grams of solid ferric chloride. The mixture was stirred for 1hour at an average temperature of 45 C. A light colored solid resin wasprecipitated from solution with methyl alcothat required in the case ofthe catalysts used v heretofore.

3. The resin is ver much lighter in color. This hol. Combinations ofcatalysts are also preferred. Thus, the combination of one mole of eachof ferric chloride and silicon tetrachloride is more active than eithercomponent by itself,

' Example 2 In a specific example of such combinat1on,'300 grams ofcyclopentadiene was stirred with 10 grams of solid ferric chloride at 25C. There was no exothermic reaction for 10 minutes, but upon addition of/2 c. c. of silicon tetrachloride, the temperature rose to the boilingpoint and it was necessary to cool the reaction mixture.

The amount of catalyst employed in the reaction ma vary over aconsiderable range, but preferably does not exceed about 1%, and seldomif ever should exceed 2% or 3%. Use of amounts greater than this resultin the formation of excessive amounts of insoluble rubber-like products.

Lower amounts of catalyst may be employed, but

of course excessive reduction of the amount is likely to result in unduereduction of the speed of the reaction. Probably the amount should notbe materially less than about one or two-tenths of one per cent. Thereaction comes to an end usually within a period of about one-half toone hour. The color of the solutions may be improved by treating themwith activated charcoal.

The resultant resin solution may be treated with alcohol, acetone, orthelike to precipitate the resin. The solvent can also be removed byevaporation if desired. Treatment of the resin solution with alcohol oracetone results'in the removal of all or most of the catalyst employed.The resultant resin may likewise be treated with a basic substance toprecipitate or inactivate the catalyst and remove at least a part of thecolor of the resin solution at this point. Thus ammonia gas may bepassed into the solution or organic bases such as morpholine, triamylamine, diethyl amine, etc. may be added.

The product is resinous in character and of light color. It readilydissolves in hydrocarbons such as toluol or xylol, and petroleum orhydrogenated petroleum, which is in contradistinction to the resinswhich have heretofore been produced at lower temperatures, and which arequite insoluble in these materials, The resin does not degenerate ordeteriorate into a powdery material uponexposure to the atmosphere.

Solutions of the resin in hydrocarbon solvents are of low viscosity andexcellently adapted for spraying or for application by other methods.Solutions when applied as varnish films to surfaces of wood, metal, orthe like, form uniform films which dry quickly, and which upon exposureto the atmosphere are soon oxidized to hard, highl adherent state.Oxidation and resultant hardening are promoted by subjecting bodiescoated with the resin, to baking at a suitable temperature, e. g., about200 to 300 F. Such baking,

of course, tends to soften the resin during operation and thus promotesflow to provide highly smooth and uniform coatings.

The resins are highly adherent to sheet metal such as iron or steel, andwhen so applied show no reaction with the base metal. Therefore, theyare excellently adapted for coating beer cans, and cans for foods of alltypes. They are also useful as coatings for pipe lines and containersfor chemical products. Surfaces of iron may receive preliminary coatingsof a phosphatic material such as zinc phosphate, in order to promoteadherence and to obviate the possibility of rusting of the surfacespreliminary to application of the resin coating. Application of coatingsof the new resins, to metallic surfaces in order to provide primingfilms for the reception of coatings of other resins, such as thecopolymer of vinyl acetate and vinyl chloride, or cellulosic materialsuch as cellulose acetate, cellulose nitrate, acetyl cellulose, benzylcellulose, and the like of course is permissible.

The resins may be incorporated with various plasticizers including amyland diamyl naphthalene, dimethoxy tetraethylene glycol, triethyleneglycol dihexoate and the like. However, the resins are of relativelyflexible character, and in many cases require little or no plasticizer.The hardened resins may be formed by heat and pressure into rods, sheetsand other forms. They may also be admixed with fillers and pressed inthe same manner as phenolic resins.

It has been found that it is not possible to mechanically combine atordinary temperatures a vegetable or animal glyceride such as soya beanoil, linseed oil, fish oil or China-wood oil with the. resins hereindescribed. However, when the glyceride is made a part of the charge, i.e., when the cyclopentadiene is polymerized in the presence of theglyceride, the said glyceride will become chemically united with andwill become a part of the resinous composition. Such a resin compositionpossesses greater flexibility than one made from unmodifiedcyclopentadiene. Instead of a glyceride, the free acid hydrolysisproducts of glycerides may be used. Thus it is possible to substitutesoya acids for soya bean oil, linseed acids for linseed oil, etc.

Examples of various charges which can be used are:

Example 3 Cubic centimeters Cyclopentadiene 4210 Xylol v 3050 Anyunsaturated vegetable oil can be used; also any product in which avegetable oil is present in some degree or combination such as in thealkyd resins or varnishes. The following charges illustrate some of themixtures which were polymerized with stannic chloride ordihydroxyfluoboric acid or boron fluoride-ethyl ether complex at 50 C.average reaction temperature:

The-product of this reaction is compatible with vegetable oils.

The varnish comprises 12 /270 ester gum. ee /2% oil and 52% thinner.

Example 9 Cubic centimeters Cyclopentadiene 3850 Soya bean oil 475 Xylol2875 Example 10 Cubic centimeters Cyclopentadiene 3400 Corn oil orcottonseed oii 450 Xylol 2600 Example 11 Cubic centimetersCyclopentadiene 2280 Tung oil.. Bodied together for 1853 Linseed oil 1%hours at 540 F. 3706 0 This mixture was polymerized with 70 grams BF;

(CzHs)-.-0.

Example 12 Cubic centimeters Cyclopentadiene 4170 Soya oil 2835 Thismixture was polymerized with BFa (Cal-Is) 20. Other types of oils may bepolymerized with cyclopentadiene. An example of such is as follows:

. Cubic centimeters Cyclopentadiene 150 Dehydrated'castor oil 5. Themixture was polymerized with dihydroxy fluoboric acid as a catalyst.

Cyclohexadiene may be substituted for cyclopentadiene .and conjointlypolymerized with vegetable oils as above described in connection with 0cyclopentadiene.

Cyclohexadiene may also be polymerized by itself in the same manner ascyclopentadiene. Such polymers are compatible with resin or oil, such aslinseed or other oil, depending upon which predominates and oils may beused interchangeably. This procedure aii'ords a new means ofincorporating hydrocarbons with vegetable oils. It may be possible touse these oil resins to prepare varnishes in the usual manner by heatingwith gums and more oil. The oils impart flexibility to the resin.

Valuable resins may be prepared by heating the dicyclo and glyceride ina closed system at above 200 C. and preferably at 230 to 260 C. for fromone to ten hours, preferably about two hours.

The following charges are representative of useful mixtures'from whichthese resins were prepared:

Cubic centimeters A charge containing relatively large amounts of tungoil requires less time and lower temperatures than a charge containingsoya or linseed oils. When the ratio of tung oil to dicyclo is greaterthan 1 to 1, there is danger of forming an insoluble gel. This danger isnot apparent when there is present some oil such as linseed,

or soya oil in which case the ratio of tung oil to dicyclo may be raisedat will. Oils may be raw, bodied, blown, refined, dehydrated, etc.; ingeneral, all natural or treated glycerides are useful. Oil acids orpartially hydrolyzed oils are also useful. The reaction time must bepredetermined and is governed by the rate of bodying of the oil and thebody desired in the finished resin.

The heating may be carried out in any convenient manner such as heatingin a glass or steel reaction bomb or autoclave. A preferred methodconsists in pumping the reacting mass through heated coils from aninsulated tank which contains the bulk of the charge. The finishedviscous resin may be withdrawn while hot and thinned with the desiredsolvent.

This process has the advantage of a one-step process and produces aresin having good light stability, toughness, light color on baking, andshort drying time. The resins are soluble in the common cheaperhydrocarbon thinners, are well adapted as varnishes or as enamelvehicles, and can be applied in the same manner as existing varnishes.They are responsive to the addition of driers in the same manner as avarnish.

Useful pigmented compositions are made as shown by the followingexamples:

Heating I (These two enamels dry to give tough white coatings havinggood light stability.)

go sea 1 part antimony oxide 5 /250 C 1 part Titanox G 1000 cc. dicycl pn a 55 part carbon black This gray enamel can be used for both airdryingand baking types of finishes. The use of these resins is not limited toany particular type etc. Driers may be added either to the charge ofpigment. The resins can be used as vehicles for aluminum, zinc paints,gilsonite, lithopone,

and be processed with the resin or may be incorporated with the finishedvehicle or enamel paste. Certain metallic soaps such as cobalt, nickel,zinc or copper 'naphthenates, or the salts of the acids derived fromnatural glycerides are useful as addenda to the charge to increase thebody of the resin. These salts then act as driers when the films aresubjected to drying conditions.

When pure dicyclopentadiene is the only by drocarbon in the charge, theresin will usually be a semi-plastic mass which must be thinned for use.This is preferably done while the resin is hot. Any hydrocarbon thinneris useful for this purpose. The charge may contain diluting materialswhich are normally present in commercial dicyclopentadiene such aslndene and coumarone, which are useful modifying agents for resins ofthis class. The most useful resins are formed, however, when at least 50per cent of the hydrocarbon charge comprises dicyclopentadiene. Othernon-resinifying diluents are permissible or these may be added duringany stage of the resinification reaction to reduce the viscosity.

The method of forming solutions of glyceride oils and cyclopentadiene byemploying a vegetable or similar glyceride oil as an absorption mediumfor cyclopentadiene generated by cracking dicyclopentadiene is referredto in my companion case, Preparation of cyclopentadiene fromdicyclopentadiene, filed March 16, 1940, Serial No. 324,391.

It is to be understood that any of the oils or free fatty acids of oilsherein mentioned may be employed as absorption media in the processdisclosed in the companion case, and the oil, when adequately saturated,may be subjected to polymerization as herein described.

Absorption of cyclopentadiene in the cracking process may also be haltedbefore completion and a quantity of cyclopentadiene may be added toobtain desired proportions. Subsequently, this solution is polymerized.

Suitable embodiments of apparatus for conducting the polymerization ofcyclopentadiene on a commercial scale are disclosed in the drawings inwhich Figures 1, 2, and 3 are diagrammatical views illustrating threedifferent forms which the apparatus may take.

In the apparatus disclosed in Figure 1 a reaction chamber 10 ofcolumn-like form is provided with an agitator ll including a shaft 12carrying agitator blades 1 3 and projecting at its upper extremitythrough a suitable packing (not shown) in the top of the reactionchamber, for connection to any convenient drive mechanism (not shown).The column is enclosed by a jacket including upper section I4 and lowersection 16. The former section is provided at its upper extremity withan outlet I! for a temperature regulating fluid which may be admitted atthe bottom of the section by means of a conduit 18 having branches l9and 2 I, leading respectively to sources of heating and cooling medium.Valves 22 and- 23 in the branches provide means for controlling theadmission of the heat-controlling fluid.

Similarly, section l6 of the jacket is provided with an outlet 24 and aninlet 25 for fluid, the inlet being branched as indicated at 21 and 28to admit of quick change from hot to cold fluid as may be required.

cyclopentadiene, in a solvent such as toluene, is fed to the top of thereaction column I o by means of conduit 29 leading to torage tank 3|,

having an inlet 32 by means of which the supply of cyclopentadiene maybe replenished from time to time. Reaction chamber I is also provided atits upper extremity with conduit 33 leading to an expansion chamber 84within which is dis posed a cooling coil 36 having inlet 81 and outlet88. Catalyst for the reaction is stored in a chamber 89 connected bymeans of conduit 4| to the top oi. the reaction chamber.

Thermometers 42 and 43 are connected to the reaction chamber in suchmanner as to admit or observation of the temperature within the'latter.An outlet conduit 44 at the bottom of the reaction chamber providesmeans for withdrawing the polymerized product continuously or from timeto time as may be desired.

In the operation of the apparatus cyclopentadlene or any one of themixtures .of cyclopentadiene and solvent or reactive glyceride oilherein disclosed from storage chamber 3| is admitted to reaction chamberIII while the upper section of preferred to speed up the reaction, asolution of cyclopentadiene of greater than concentration may be fed tothe reaction chamber and the temperature allowed to rise to about 60 C.In the latter case there will be substantial ebullition throughout thereaction mixture and it rises into the expansion chamber 34 where it iscooled by the coil 86. It will be apparent that in event the ebullitionis not too violent the vapors merely pass upwardly into the expansionchamber and the latter acts as a reflux condenser.

When the reaction with the chamber I8 has passed its peak, both sectionsof the jacke may be heated in order to efiect a cure of the fluid resincontained therein. During this curing stage additional catalysts may beadded.

In the apparatus shown in theFigure 2 an initial reaction chamber 50 isprovided with cooling coil 5| having inlet 52 and outlet 53 for heatingfluid. Catalyst is admitted to the chamber through inlet 54 andcyclopentadiene to be polymerized is admitted through conduit 56. Thetwo materials are admixed within the chamber by means of agitator 5'1.The temperature fluctuations in the chamber are determined by means of athermometer 58. The reactants within the chamber may be drawn off ifdesired through conduit 58, but preferably are flowed ofi throughconduit 5| to a second reaction chamber 62. This flow may be by gravityor may be assisted 'by means of a suitable pump 63. Reaction chamber "iscooled by means of a coil 64 through which an appropriate cooling mediumis circulated. An agitator 65 is also provided. The course of thereaction within the chamber is determined by observation of thermometer88 which is connected to the chamber in conventional manner. Thereaction product from the chamber 62 may be withdrawn to storage throughconduit 61 or it may be recycled through conduit 68, pump 69 and conduitII to the initial reaction chamber 50. In the latter, additionalcatalysts may be added and the resin subjected to heat in order toeffect a ilnal cure. The finished product is withdrawn through theconduit 59. Catalyst may be added through conduits 12.

The mode of operation of the apparatus is substantially self-evident.The reactants are simply introduced into chamber 50, heated to atemperature of about 40 to 60 C. until reaction has :progressedsufliciently far to induce exothermic temperature rise. The mixture ofcatalysts and resin is then withdrawn to chamber 62 where thetemperature is maintained at the desired value until the peak of thereaction has passed, as evidenced by the tendency of the reactants tocool. Subsequently the materials are recycled to chamber 50 whereadditional catalyst is added and the material heated in order to effecta final cure.

In the form of the apparatus disclosed in Figure 3, the catalyst and thecyclopentadiene are admixed cold and the cold mixture is employed insuch manner as to obtain regulation of the temperature in the reactionchamber. The apparatus embodies a suitable reaction column "which may bepacked with carbon rings, steel chips, or similar packing materials 15.The charge for the column is contained in chamber 16 which is pro- Ivided with a cooling coil 11, and an inlet 18 for replenishment of thecharge. The cyclopentadiene after cooling is admitted through conduit 19and pump 81 to the top of the reaction column. The column is suppliedwith catalysts through conduit 82. Inlet conduit 83 at the bottom of thecolumn :14 provides means for admission of additional catalyst. Partialpolymerized cyclopentadlene after the reaction has passed its peak maybe withdrawn from the chamber 14 through conduit 84 at the bottomthereof and fed by pump 85 through conduits 86' and 81 to a curingchamber 88, which is suitably heated by coil 89 through which fluid isconducted, or if preferred it may be recycled by the pump throughextension 9i of conduit 86 to the top of column 14. Valves 92 providemeans for determining the course of flow of the reactants.

In the operation of this embodiment of the apparatus, coldcyclopentadiene is introduced at the top of column 14 where it isadmixed with catalysts that flows downwardly through the. packing 15. Inthe bottom of the chamber the-mixture of cyclopentadiene, in thepresence of the catalyst, reacts exothermically and as the reactiontemperature tends to rise, cold charges is introduced from the storagetank. This cools the reacting liquids and checks the violence of thereaction. When the charge in the bottom of the colunm is approximately75% polymerized, additional catalyst is added through conduit 83 and themixture withdrawn through conduit 84. The partially reacted resin mayoptionally be recycled through conduit 9| to the top of the chamber 15or through conduit 81 to chamber 88. In the latter it is subjected to acuring temperature by circula-' tion of heatingfluid through COil 89.

This is a division of my copending application I Serial No. 324,392,filed March 16, 1940, for Resinous material.

Although certain forms of the invention have been described herein, itwill be apparent that these are merely exemplary, and that numerousmodifications may be made therein without departure from the spirit ofthe invention, or the scope of the appended claims.

What I claim is:

1. A process of preparing a resinous material which comprises heating amixture of dicyclopentadiene and an unsaturated glyceride oil to atemerature of about 200 to 260 C. for a period of closed container.

2. A process of preparing a. resinous material which comprises heating amixture of an unsaturated glyceride oil and dicyclopentadlene in aclosed container and in the absence oi catalysts of polymerization to atemperature of about 200 to 260 C. until a copolymer soluble inhydrocarbon thinners is formed.

3. A process of preparing a resinous material which comprises heating amixture of dicyclo entadiene and an unsaturated glyceride oil to atemperature above about 200 C. in the absence of catalysts ofpolymerization and in a closed container until a conjoint polymer of thecomponents of the mixture soluble in hydrocarbon thinners is formed.

4. A process of preparing a resinous material which comprises heating amixture of dicyclopentadiene and a drying glyceride oil to a temperatureabove about 200 C. in the absence of catalysts of polymerization and ina closed container until a copolymer soluble in hydrocarbon thinners isformed.

5. A process of preparing a resinous material which comprises heating amixture of dicyclopentadiene and linseed oil to a temperature aboveabout 200 C. in a closed container and in the absence of catalysts ofpolymerization until a conjoint polymer soluble in hydrocarbon thinnersis formed.

6. A process of preparing a resinous material which comprises heating amixture or dicyclopentadiene and tung oil in a closed container and inthe absence of catalysts of polymerization to a temperature above 200 C.until a conjoint polymer soluble in hydrocarbon thinners is formed.

7. A process of preparing a resinous material which comprises subjectinga mixture of dicyclopentadiene and soya bean oil to conjointpolymerization by heating said mixture in a closed container in theabsence of catalysts of polymerization to a temperature above about 200C. until a resinous product soluble in hydrocarbon thinners is formed.

8. A process of preparing a resinous material which comprises subjectinga mixture of dicyclopentadieneand tung oil to conjoint polymerization byheating them in a closed container and in the absence of catalysts ofpolymerization to a temperature approximately within the range of 200 to260 C. for a Period of about 1 to 10 hours until a copolymer soluble inhydrocarbon thinners is formed.

HOWARD L. GERHART.

